WO2013111753A1

WO2013111753A1 - Method for producing epoxidized natural rubber, rubber composition for tires, and pneumatic tire

Info

Publication number: WO2013111753A1
Application number: PCT/JP2013/051208
Authority: WO
Inventors: 榊　俊明; ルクサナポーンタラチウィン; カモルチャトチャルンチタリー; ハターイナットクムオーム
Original assignee: 住友ゴム工業株式会社
Priority date: 2012-01-23
Filing date: 2013-01-22
Publication date: 2013-08-01
Also published as: CN104053677A; CN104053677B; EP2808347A4; US20140378619A1; US9193806B2; EP2808347B1; EP2808347A1

Abstract

Provided are: a simple and easy method for producing a relatively uniform epoxidized natural rubber at low cost; a rubber composition for tires, which contains the epoxidized natural rubber; and a pneumatic tire which is produced using the rubber composition for tires. The present invention relates to a method for producing an epoxidized natural rubber, which comprises: a step (1) wherein a granular solid rubber is prepared by solidifying a natural rubber latex into granules; and a step (2) wherein the thus-obtained granular solid rubber is treated with an epoxidation liquid so that the granular solid rubber is epoxidized.

Description

Process for producing epoxidized natural rubber, rubber composition for tire and pneumatic tire

The present invention relates to a method for producing an epoxidized natural rubber, a tire rubber composition using the epoxidized natural rubber obtained by the production method, and a pneumatic tire.

Conventionally, epoxidized natural rubber has been used in rubber products such as tires, and this epoxidized natural rubber is generally a process of concentrating field latex collected from rubber trees such as Hevea brasiliensis by centrifugation. , Adding a surfactant to the concentrated latex obtained, adding formic acid while stirring, slowly adding hydrogen peroxide over several hours, and allowing the epoxidation reaction to proceed for about 1 day, resulting latex The epoxidized natural rubber is coagulated, and the coagulated natural rubber latex is neutralized, washed with water and dried as necessary.

According to this series of manufacturing processes, the rubber is epoxidized with the size (0.1 to several μm) existing in the latex, so there is a merit that the rubber is uniformly epoxidized, but the reaction takes a long time. There is a problem that the production cost of the epoxidized natural rubber is very high due to the necessity, the use of expensive chemicals, and the large number of processes. In addition, the rubber becomes unstable and hardens and requires a surfactant, which increases the cost, and if the surfactant remains in the final rubber product, the rubber properties deteriorate due to water absorption, making it difficult to control the temperature of the epoxidation reaction. However, there is a problem that the worker needs to monitor constantly.

On the other hand, Patent Document 1 discloses a method for preparing epoxidized natural rubber latex by preparing peracetic acid from acetic acid and / or acetic anhydride and hydrogen peroxide, and then mixing the peracetic acid and natural rubber latex. According to this, the chemical reaction proceeds promptly and quantitatively, and a desired epoxidation rate can be reached quickly. However, in this method, the reaction between acetic acid or acetic anhydride and hydrogen peroxide requires excessive acetic acid and hydrogen peroxide in order to obtain the peracetic acid required for the equilibrium reaction. In addition, there is a problem that the cost for waste water treatment of excessive chemicals is also required.

JP 2009-293011 A

The present invention solves the above problems and uses a simple, inexpensive and relatively uniform method for producing epoxidized natural rubber, a tire rubber composition containing the epoxidized natural rubber, and the tire rubber composition. It aims at providing the produced pneumatic tire.

The present invention includes a step 1 for solidifying a natural rubber latex into a granular form to prepare a granular solid rubber, and a step 2 for treating the obtained granular solid rubber with an epoxidizing liquid and epoxidizing the granular solid rubber. The present invention relates to a method for producing an epoxidized natural rubber.

The epoxidation liquid is preferably a peracetic acid-containing liquid and / or a formic acid-containing liquid. Here, the peracetic acid-containing liquid is preferably one obtained by mixing and reacting acetic acid and / or acetic anhydride and hydrogen peroxide, and the formic acid-containing liquid includes formic acid and hydrogen peroxide. What is obtained by mixing and reacting is preferable.

As the natural rubber latex, it is preferable to use at least one selected from the group consisting of field latex, concentrated latex obtained by concentrating field latex, and modified natural rubber latex obtained by removing non-rubber components therefrom.

The step 1 is preferably a step of coagulating the natural rubber latex into particles using an acid to prepare a granular solid rubber, and coagulating the natural rubber latex into particles using an acid and a flocculant, More preferably, it is a step of preparing a solid rubber.

The particle size of the granular solid rubber is preferably 20 mm or less, and more preferably 12 mm or less.

The present invention relates to an epoxidized natural rubber obtained by the above-described production method.
Here, the epoxidized natural rubber preferably has an epoxidation degree of 0.1 to 50%.

The present invention relates to a tire rubber composition containing the epoxidized natural rubber.
The present invention also relates to a pneumatic tire produced using the tire rubber composition.

According to the present invention, natural rubber latex is solidified into a granular form to prepare a granular solid rubber, and the obtained granular solid rubber is treated with an epoxidizing liquid to epoxidize the granular solid rubber; Therefore, the epoxidized natural rubber can be produced easily, at a low cost, and relatively uniformly as compared with the conventional production method.

Specifically, by epoxidizing a granular solid rubber produced by coagulating natural rubber latex into particles, expensive chemicals used for epoxidation can be reused without waste, and reagents necessary for epoxidation can be reused. Loss can be eliminated. Moreover, since it is the manufacturing method which epoxidizes the granular solid natural rubber with a very large surface area, a comparatively uniform epoxidized natural rubber is obtained. Furthermore, the ratio of the waste liquid to the amount of rubber production is very small compared with the case of epoxidizing from latex, and it is not necessary to use various chemicals, so that it is possible to reduce the environmental burden.

[Method for producing epoxidized natural rubber]
The method for producing an epoxidized natural rubber according to the present invention comprises a step 1 of coagulating a natural rubber latex into a granular form to prepare a granular solid rubber, and treating the obtained granular solid rubber with an epoxidizing liquid, And epoxidizing step 2.

In the conventional method of epoxidizing field latex collected from natural rubber trees, the entire process up to the epoxidation process is performed under liquid conditions, then the rubber is solidified, the remaining acid is neutralized with alkali, and washed. An epoxidized natural rubber is prepared by performing a drying process. That is, in such a manufacturing method, the chemical used for epoxidation remains in the rubber almost as it is, and the residual chemical is washed away in the cleaning process, so that the chemical is used once and never reused. In addition, the washing waste water contains unreacted formic acid and hydrogen peroxide, and waste liquid treatment for neutralizing the acid and decomposing the hydrogen peroxide is also necessary.

On the other hand, in the production method of the present invention, the granular solid rubber obtained by coagulating natural rubber latex in a granular form is treated with an epoxidizing liquid capable of epoxidizing rubber, for example, acetic acid or acetic anhydride. Immersing a granular solid rubber in an epoxidized liquid such as a peracetic acid-containing liquid produced by blending hydrogen peroxide or a mixed liquid (formic acid-containing liquid) in which formic acid and hydrogen peroxide are blended, the epoxidized liquid The epoxidation of the rubber is progressed, for example, by spraying into a solid rubber solid. Therefore, unlike the conventional epoxidation process under liquid conditions, it is possible to recover the epoxidation liquid used for dipping or spraying. Peracetic acid and performic acid are instantly epoxidized when natural rubber (both solid and latex) is present in the vicinity. At the same time, the rubber returns to acetic acid and formic acid. By adding acetic acid, formic acid or hydrogen peroxide to the mixture, peracetic acid or formic acid can be generated again. In addition, unlike latex, moisture hardly increases, and the liquid is hardly diluted, so that expensive chemicals used in the processing liquid can be reused. In addition, since it is reusable, there is almost no drainage, so there is no need for wastewater treatment, and there are advantages in both cost and environmental impact. In addition, since the temperature of the reaction solution cannot be controlled and there is no fear that the entire latex is hardened, it is unnecessary to closely monitor the worker during the reaction, which contributes to cost reduction.

In the modified natural rubber from which the non-rubber component is removed, the epoxidized natural rubber can be produced by a simple technique of adding an epoxidation step to the production process.

Furthermore, in the present invention, a granular solid rubber having an overwhelmingly large surface area is prepared and epoxidized, so that a relatively uniformly epoxidized rubber can be prepared. Although the latex state has the largest surface area, the epoxidation agent cannot be reused as described above, and therefore the production method of the present invention in which the latex is solidified in a granular form is desirable.

Therefore, according to the present invention, an epoxidized natural rubber that has been epoxidized relatively uniformly can be produced in a short time and easily with a small number of steps, and the chemicals used in the epoxidized liquid can be reused during the production. This eliminates chemical loss, reduces waste liquid treatment costs and environmental burdens, and eliminates the need for strict monitoring of the worker during the reaction.

(Process 1)
In step 1, natural rubber latex is solidified into a granular form to prepare a granular solid rubber.
It is generally known that natural rubber latex coagulates with the addition of acid or salt. This is because latex particles have a peak particle size of 1 μm, the surfaces are negatively charged and repel each other, and exist stably in the serum, but this negative charge is present in acids and salts. If it is weakened by cations and the amount of latex is sufficiently large, the rubber will aggregate at once and become a large lump of 10 cm or more. In such a state, the surface area of the rubber becomes very small with respect to the weight, and even if it is epoxidized, it reacts very little, so that the modification is virtually impossible. Even if it is solidified little by little to avoid this, when it is carried out on an industrial scale, if it is transferred to a tank, the rubbers stick together and eventually become a large lump. On the other hand, the present invention is a method for epoxidizing granular natural rubber produced by coagulating rubber in natural rubber latex into particles, so that an epoxidized natural rubber having a large surface area and uniformly epoxidized is obtained. can get.

As natural rubber latex, raw latex (field latex) collected by tapping natural rubber trees such as Hevea tree, concentrated latex (purified latex, ammonia by conventional methods) concentrated by centrifugation or creaming method. High-ammonia latex, zinc oxide, TMTD, and ammonia-stabilized LATZ latex), non-rubber components such as proteins and phospholipids removed from these latexes, and saponified natural rubber latex Modified natural rubber latex such as can be used. Here, deproteinized natural rubber latex and saponified natural rubber latex can be prepared by a known method such as proteolytic enzyme or saponification treatment with alkali.

Examples of a method for preparing a granular solid rubber by coagulating a natural rubber latex include a method for controlling the pH of the natural rubber latex. Particularly, in order to produce rubber particles having a small particle diameter, natural rubber latex is used. A method in which the flocculant is added under the condition of controlling the pH of is preferable.

The pH control (pH adjustment) is preferably 3.0 to 5.0, more preferably 3.5 to 4.5. By adjusting the pH within the above range, particulate rubber (granular solid rubber) can be obtained. The pH can be controlled with an acid such as formic acid, acetic acid or sulfuric acid, or an alkali such as sodium hydroxide or potassium hydroxide, and it is preferable to use an acid.

As the flocculant, a polymer flocculant or the like can be used. Examples of polymer flocculants include cationic polymer flocculants such as methyl chloride quaternary salt polymers of dimethylaminoethyl (meth) acrylate, anionic polymer flocculants such as acrylate polymers, and acrylamide polymers. And a nonionic polymer flocculant such as a methyl chloride quaternary salt-acrylate copolymer of dimethylaminoethyl (meth) acrylate. Among these, a cationic polymer flocculant is preferable because it is possible to efficiently obtain a granular rubber, and a poly (meth) acrylic acid ester based polymer such as a polymer of dimethylaminoethyl (meth) acrylate methyl chloride quaternary salt. Is more preferable, and a polymer of dimethyl quaternary salt of dimethylaminoethyl (meth) acrylate is more preferable. As the cationic polymer flocculant, any of strong cationic, medium cationic and weak cationic can be used, but strong cationic polymer flocculants are preferred.

The lower limit of the addition amount of the flocculant is preferably 0.05 parts by mass or more and more preferably 0.1 parts by mass or more with respect to 100 parts by mass of the solid content of the natural rubber latex. If it is less than 0.05 parts by mass, the amount added is insufficient, and there is a possibility that a granular solid rubber can be obtained only partially. The upper limit is preferably 5.0 parts by mass or less, and more preferably 1.5 parts by mass or less. When the amount exceeds 5.0 parts by mass, the amount of the aggregating agent adsorbed on one particle becomes too large, and the particles may be dispersed by the repulsive action between the particles, and the aggregate may not be obtained. Furthermore, it is not economical from an economic point of view.

Step 1 may be performed in the presence of a surfactant because the granular solid rubber is well prepared. As the surfactant, an anionic surfactant, a nonionic surfactant, and an amphoteric surfactant can be used. Examples of the anionic surfactant include carboxylic acid-based, sulfonic acid-based, sulfate ester-based and phosphate ester-based anionic surfactants. Examples of nonionic surfactants include nonionic surfactants such as polyoxyalkylene ethers, polyoxyalkylene esters, polyhydric alcohol fatty acid esters, sugar fatty acid esters, and alkyl polyglycosides. Examples of the amphoteric surfactant include amphoteric surfactants such as amino acid type, betaine type, and amine oxide type. Among these, an anionic surfactant is preferable, and a sulfonic acid anionic surfactant is more preferable.

The surfactant does not need to be added in particular, but when added, the addition amount is preferably 0.1 parts by mass or more, and 0.2 parts by mass with respect to 100 parts by mass of the solid content of the natural rubber latex. The upper limit is preferably 5.0 parts by mass or less, and more preferably 2.0 parts by mass or less. By adjusting within the above range, a granular solid rubber can be obtained satisfactorily.

Granular solid rubber is obtained by Step 1, but the particle diameter is preferably 20 mm or less, more preferably 12 mm or less, still more preferably 10 mm or less, and particularly preferably 5 mm or less. By strictly controlling the pH and, if necessary, adding a flocculant under appropriate stirring conditions, the rubber is solidified into granules, and rubber particles having the above particle diameter can be obtained. The lower limit of the particle diameter of the granular solid rubber is not particularly limited, and the smaller the particle diameter, the more suitable, but usually 0.1 mm or more. The particle diameter can be measured by visual observation, a micrograph or the like.

The granular natural rubber obtained in this way still contains a large amount of non-rubber components in the serum, so it may be washed with water if necessary. It may be removed under an atmosphere and then washed with water. By washing with water, the rubber particle size tends to be larger than that immediately after coagulation, but by stirring under appropriate stirring conditions, growth of the particle size is suppressed and most particles are kept to a size of several mm or less. Is possible. The technology that does not grow rubber particles greatly in the present invention is a technology that is not recognized by general latex engineers.

The washing step includes, for example, a method in which water is added to a rubber component (coagulated product), the rubber component is suspended in water while stirring for a certain period of time, solid-liquid separation is performed, and the rubber component is taken out. Solid-liquid separation may be performed using, for example, the specific gravity difference between rubber and water. Specifically, for example, after the rubber component is suspended in water, the rubber component is allowed to stand for a certain period of time, and water having a higher specific gravity than the rubber component is extracted from the lower part of the container. Centrifugation may also be performed.

(Process 2)
The granular solid rubber obtained in step 1 is treated with an epoxidation liquid to epoxidize the granular solid rubber.
The epoxidation liquid used in the present invention is not particularly limited as long as it is a liquid capable of epoxidizing a granular solid rubber produced by solidifying natural rubber latex into particles, and a peracetic acid-containing liquid, performic acid. A containing liquid etc. can be used conveniently.

The peracetic acid-containing liquid is not particularly limited as long as it contains peracetic acid or generates peracetic acid. For example, a liquid obtained by mixing and reacting acetic acid and / or acetic anhydride with hydrogen peroxide. It can be used suitably. In this case, epoxidation can be promoted by peracetic acid generated by the reaction, and the concentration of the solution after the treatment is adjusted by adding acetic acid, acetic anhydride or hydrogen peroxide to generate peracetic acid again. In addition, the processing solution can be reused.

Acetic acid and acetic anhydride are not particularly limited, and for example, glacial acetic acid or commercially available acetic acid diluted to an arbitrary concentration can be used. Considering production efficiency, acetic acid having a concentration of 80 to 100% by mass is preferable, and acetic acid having a concentration of 90 to 100% by mass is more preferable.

The hydrogen peroxide is not particularly limited, and a commercially available aqueous hydrogen peroxide solution can be used. The concentration of the aqueous hydrogen peroxide solution is preferably 10 to 60% by mass, and particularly preferably 30 to 60% by mass from the viewpoint of reaction efficiency. If the amount is less than 10% by mass, the liquid may be diluted immediately after repeated use. If the amount exceeds 60% by mass, explosion may occur. In particular, in terms of the possibility of explosion, it is preferably 50% by mass or less and close to the concentration.

A method of mixing and reacting acetic acid and / or acetic anhydride and hydrogen peroxide is not particularly limited, and a conventionally known method can be used. For example, when 30% by mass hydrogen peroxide aqueous solution and 90% by mass acetic acid are gently mixed and reacted for 1 to 2 days, peracetic acid is produced, but it does not react 100%. In this state, acetic acid coexists. When granular solid rubber is added to the peracetic acid-containing liquid in this state, peracetic acid reacts quickly with the rubber, the rubber is epoxidized, and peracetic acid returns to acetic acid. In other words, acetic acid is a catalyst, hydrogen peroxide is divided into water and oxygen, and this oxygen reacts with rubber.

Hydrogen peroxide is preferably added in an amount of 0.05 to 5 mol per mol of acetic acid and / or acetic anhydride, and more preferably 0.1 to 2 mol in view of safety and efficiency. If the amount is less than 0.05 mol, the conversion of acetic acid may be significantly reduced, which is not economical. On the other hand, when the amount exceeds 5 mol, the conversion rate of hydrogen peroxide may be remarkably lowered, which is not economical.
In order to advance the reaction quickly, it is preferable to add a small amount of an acid such as sulfuric acid.

In the peracetic acid-containing liquid after the reaction, practically no peracetic acid remains. Therefore, hydrogen peroxide and, if necessary, acetic acid or glacial acetic acid are added here, and after a period of time again, peracetic acid is generated again, which can be reacted with rubber. Can be reused. Since peracetic acid reacts quantitatively with rubber, it becomes possible to control the level of epoxidation of rubber from the amount of liquid contained and the concentration of peracetic acid.

The formic acid-containing liquid is not particularly limited as long as it contains formic acid or produces formic acid. For example, a mixed liquid of formic acid and hydrogen peroxide, formic acid and hydrogen peroxide are mixed and reacted. The liquid obtained by this can be used suitably. In this case, the epoxidation can proceed with the formic acid generated by the reaction, and the formic acid and hydrogen peroxide are added to the liquid after the treatment to adjust the concentration, and then the formic acid is generated again. Can be reused.

Formic acid is not particularly limited, and for example, commercially available formic acid diluted to an arbitrary concentration can be used. Considering production efficiency, safety, and target degree of epoxidation, formic acid with a concentration of 10 to 100% by mass is preferable, and formic acid with 30 to 94% by mass is more preferable.
The hydrogen peroxide is not particularly limited, and those similar to the above can be used.

As the formic acid-containing liquid, a liquid obtained by mixing formic acid and hydrogen peroxide in advance to form formic acid may be used. However, because formic acid is unstable, formic acid and hydrogen peroxide are mixed. It is desirable to use a liquid. Specifically, it is preferable to immerse the granular solid rubber in formic acid, and then drop and mix hydrogen peroxide in this order to form performic acid to react the granular solid rubber with the formic acid. When the solid solid rubber is put into the liquid containing formic acid mixed with formic acid and hydrogen peroxide, the formic acid reacts quickly with the rubber, the rubber is epoxidized, and the formic acid returns to formic acid. In other words, formic acid is a catalyst, hydrogen peroxide is divided into water and oxygen, and the oxygen reacts with rubber. It is also possible to use an epoxidation liquid containing both of these components by coexisting formic acid with acetic acid and / or acetic anhydride and reacting these with hydrogen peroxide to form both formic acid and peracetic acid.

Hydrogen peroxide is preferably added in an amount of 0.05 to 5 mol per mol of formic acid, and more preferably 0.1 to 2 mol in view of safety and efficiency. If it is less than 0.05 mol, the conversion of formic acid may be significantly reduced, which is not economical. On the other hand, when the amount exceeds 5 mol, the conversion rate of hydrogen peroxide may be remarkably lowered, which is not economical.
In order to advance the reaction quickly, it is preferable to add a small amount of an acid such as sulfuric acid.

In the formic acid-containing liquid after the reaction, practically no formic acid remains. Therefore, it is possible to add hydrogen peroxide and, if necessary, formic acid here, to react the resulting mixed solution with rubber, and to reuse the solution after the reaction. Since performic acid reacts quantitatively with rubber, the level of epoxidation of rubber can be controlled from the amount of liquid contained and the concentration of performic acid.

In the present invention, the granular solid rubber is epoxidized by treatment with an epoxidizing liquid.
The treatment method is not particularly limited as long as it is a method capable of bringing the granular solid rubber into contact with the epoxidized liquid, and includes immersion; spraying by spraying, showering, and the like. Specifically, as a dipping method, a method of putting granular solid rubber in a hole-shaped cage-like case, immersing it in an epoxidation solution as it is, and then pulling it up is convenient. Further, as a spraying method, there are a method of passing such a basket during the shower of the epoxidized liquid, a method of spraying a spray of the epoxidized liquid on such a basket, and the like. When these methods are used, surplus and treated epoxidation liquid can be easily recovered and reused. In addition, this makes it very easy to wash away the acid remaining on the surface, which will be described later.

Even if such a cage is not used, the epoxidation treatment can also be performed by directly putting the granular solid rubber into a normal tank charged with the epoxidized liquid and reacting it and taking it out. Specifically, when a large amount of rubber having a small particle size is contained, put agglomerated natural rubber into a tank, pour the epoxidized liquid into this tank, react it, and then extract only the epoxidized liquid from the bottom. It is possible. This is because natural rubber has a light specific gravity of 0.91 to 0.93 and the rubber floats, and the extracted epoxidized liquid can be reused as described above. This process can be carried out in batch units, or it is possible to continuously take out the rubber by continuously reacting while supplying the epoxidized liquid and the granular solid rubber. The container for the reaction may be a normal tank. Since it is in an acidic atmosphere, the surface may be coated, stainless steel, or an inert resin may be used. In order to make the whole system uniform during the reaction, stirring is desirable, but stirring is not essential.

The time for treating the granular solid rubber with the epoxidized liquid is not particularly limited as long as the desired epoxidation can proceed, and for example, it may be carried out for 1 second to 48 hours. Below the lower limit, the reaction does not tend to proceed sufficiently, and there is no problem even if the upper limit is exceeded, but the reaction is almost complete and the production efficiency is not good, and the deterioration of rubber due to residual hydrogen peroxide is prevented. To within 1 hour.

In particular, when the granular solid rubber is treated with a peracetic acid-containing liquid, the lower limit is 1 second or more, preferably 10 seconds or more, more preferably 30 seconds or more, and the upper limit is not particularly limited, but preferably within 1 hour. Is within 30 minutes, more preferably within 10 minutes. Moreover, when processing granular solid rubber using a formic acid containing liquid, a minimum is preferably 10 seconds or more, more preferably 30 seconds or more, and the upper limit is not particularly limited, but is within 48 hours, preferably 24 hours. Is within.

The treatment temperature (reaction temperature) is not particularly limited as long as the desired epoxidation can proceed, and for example, it may be carried out at 10 to 75 ° C. In particular, when the granular solid rubber is treated using a peracetic acid-containing liquid, the reaction temperature is high, so the treatment temperature does not need to be so high, and is 10 ° C. or higher, preferably 15 ° C. or higher, more preferably 20 ° C. or higher. The upper limit is not particularly limited, but the reaction proceeds sufficiently even at 30 to 40 ° C., and the reaction proceeds in a room temperature atmosphere, which is preferable from the viewpoint of energy. Moreover, when processing granular solid rubber using a formic acid containing liquid, reaction temperature is 30 degreeC or more, Preferably it is 50 degreeC or more, and the upper limit is 75 degreeC or less from a point with concern about explosive property of a formic acid. It is preferable to adjust to.

The level of epoxidation can be adjusted according to the required physical properties. Epoxidation is a reaction in which part of the double bond of natural rubber (cis-1,4-isoprene) changes as follows. The degree of epoxidation is how many of the full double bonds are epoxidized. Commercially available products have an epoxidation degree of 12.5%, 25%, 37.5%, 50%, 60%, but the epoxidation degree is not limited to these values. For example, it can be less than 1%, and the upper limit can exceed 60%. Depending on the part of the tire, about 0.1 to 50% can be used, and considering the balance of performance, the upper limit is about 30%.
The degree of epoxidation is determined by the relationship between the amount of peracetic acid or performic acid present in the liquid and the amount of double bonds in the rubber, and can be adjusted accordingly.

The epoxidized rubber thus produced is preferably washed away by immersing it in water or an aqueous alkaline solution or spraying it with a spray shower or the like. If the acid remains, the scorch may be shortened or the vulcanization may be delayed. However, since peracetic acid has already reacted with the rubber, the reaction is inhibited by washing away the acid, and the degree of epoxidation is reduced. There is no decline. In addition, when using alkaline aqueous solution, it is desirable to finally wash away with substantially neutral water.

As the alkaline aqueous solution, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, ammonia water, sodium hydroxide, potassium hydroxide and the like can be used. However, in terms of odor and safety, 0.5 to 5 can be used. % Of sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate and the like can be suitably used.

The treatment time for neutralization / washing with an alkaline aqueous solution or water is from 1 second to 1 day, preferably from 10 seconds to 4 hours, more preferably from the viewpoint of sufficiently neutralizing and washing the acid remaining on the surface. 20 seconds to 2 hours.

The rubber obtained above is appropriately subjected to a drying step as necessary, whereby the epoxidized natural rubber according to the present invention is obtained. In the drying step, the drying method is not particularly limited, and a normal TSR dryer can be used, and rubber can be placed on a belt conveyor and dried with hot air. Although not generally used, heating by microwave and vacuum drying are also possible. It is also possible to make rubber into a sheet shape with a creper or the like and dry it as it is.

The drying temperature is not particularly limited, and drying is usually possible at room temperature or higher, but considering productivity, it is 60 ° C. or higher, preferably 70 ° C. or higher, more preferably 80 ° C. or higher. Further, the upper limit is 140 ° C. or lower, preferably 135 ° C. or lower, more preferably 130 ° C. or lower, because the rubber is likely to deteriorate when the temperature is high. The drying time may be set as appropriate according to the drying temperature. In addition, since heat resistance tends to be lower than that of normal natural rubber due to epoxidation, a lower value is preferable as long as productivity is not hindered.

The method of treating the granular solid rubber of the present invention with an epoxidizing liquid and epoxidizing it produces a fairly homogeneous finish, but the tendency of the rubber surface to be epoxidized remains as compared with the method of epoxidizing latex. However, when the resulting rubber is used alone or blended with another rubber, such as natural rubber or SBR, the affinity between epoxidized natural rubber and silica is improved, especially in the case of silica compounding, and the dispersibility of silica is also improved. Thus, tan δ is reduced and rubber strength is improved. The effect is comparable to expensive epoxidized natural rubber made from latex, but can be greatly reduced in cost.

[Manufacturing method of other epoxidized natural rubber]
As a method for producing the epoxidized natural rubber of the present invention, in addition to the above-mentioned method, a production method including a step of treating a solid rubber coagulated with a natural rubber latex with an epoxidizing liquid and epoxidizing the solid rubber may be mentioned. .

In the other production method, the epoxidation of the rubber is advanced by treating the solid rubber obtained by coagulating the natural rubber latex with an epoxidizing liquid capable of epoxidizing the rubber. Therefore, unlike the conventional epoxidation process under liquid conditions, it is possible to recover the epoxidation liquid used for dipping or spraying. Peracetic acid and performic acid are instantly epoxidized when natural rubber (both solid and latex) is present in the vicinity. At the same time, the rubber returns to acetic acid and formic acid. By adding acetic acid, formic acid or hydrogen peroxide to the mixture, peracetic acid or formic acid can be generated again. In addition, unlike latex, moisture hardly increases, and the liquid is hardly diluted, so that expensive chemicals used in the processing liquid can be reused. In addition, since it is reusable, there is almost no drainage, so there is no need for wastewater treatment, and there are advantages in both cost and environmental impact. In addition, since the temperature of the reaction solution cannot be controlled and there is no fear that the entire latex is hardened, it is unnecessary to closely monitor the worker during the reaction, which contributes to cost reduction.

Furthermore, epoxidized natural rubber can be produced by a simple method of adding an epoxidation step to the normal TSR production step.
Therefore, according to the other production method, the epoxidized natural rubber can be produced easily in a short time with few steps, and the chemical used in the epoxidized liquid can be reused during the production. Loss can be eliminated, waste liquid treatment cost and environmental load can be reduced, and strict monitoring of the worker during the reaction is also unnecessary.

(Solid rubber)
In the other production method, the same natural rubber latex as described above can be used.
Examples of the solid rubber obtained by solidifying the natural rubber latex include a cup lamp, an unmade sheet (unsmoked sheet: USS), and a cup lamp solidified with field latex (slab).

As a cup lamp, natural rubber latex is collected in a cup that collects natural rubber, and natural rubber that is naturally coagulated by fatty acids generated by the decomposition of non-rubber components by microorganisms, or chemicals that have a function of coagulating natural rubber latex in advance. Natural rubber that has been put in a cup and forced to coagulate quickly. The chemical is not particularly limited as long as it has such a function, for example, an acid such as sulfuric acid, formic acid, hydrochloric acid or acetic acid, a cation such as calcium ion or a salt thereof, an organic such as methanol or ethanol. A solvent etc. are mentioned. This cup lamp literally has the shape of a cup and contains dust. For this reason, even if epoxidized as it is, only the outermost surface is epoxidized, and the ratio of epoxidation in the whole rubber becomes low. Therefore, in the present invention, it is preferable to use a chopped solid rubber.

Cup lamps are usually processed into technically graded rubber called TSR, and in the process, they are repeatedly shredded and washed with machines such as prebreakers and hammer mills, and the thickness of the rubber is reduced by multiple crepers. Thus, impurities contained in the rubber are washed away, and further water-soluble substances are removed. This is finally cut into a size of 2 to 3 mm or less by a machine called a shredder and then dried. In this state, since the rubber has a very large surface area, many parts in the solid rubber are epoxidized by treatment by immersion in the epoxidized liquid or spraying of the epoxidized liquid. If epoxidation is performed with a small surface area (in the form of a large lump), the surface epoxidation proceeds excessively and the internal epoxidation does not proceed. Therefore, the modified parts are hard aggregates when the resulting rubber is kneaded. There is a risk of becoming. In addition, since there is no concern that the rubber solidifies during epoxidation, it is not necessary to pay close attention to the control of the reaction temperature, and the process can be automated.

(Epoxidation liquid)
The epoxidation liquid used in the other production method is not particularly limited as long as it is a liquid capable of epoxidizing a solid rubber produced by coagulating natural rubber latex, and the peracetic acid-containing liquid described above, A performic acid-containing liquid or the like can be suitably used.

(Epoxidation process)
In the other manufacturing method, the solid rubber is treated with an epoxidation liquid to be epoxidized.
The treatment method is not particularly limited as long as it is a method capable of bringing the solid rubber and the epoxidized liquid into contact with each other, and the same method as described above can be used, and the treatment time and the treatment temperature can be carried out under the same conditions.

Further, as the epoxidation step in the other production method, a method of epoxidizing the solid rubber while kneading the solid rubber and the epoxidized liquid can also be used. That is, for example, the solid rubber and the epoxidized liquid can be put into a mixer such as a kneader or an extruder, and the solid rubber can be epoxidized while kneading these materials. In particular, when chopped solid rubber is used, the internal ratio to the rubber surface is high even in the chopped state, but the effect of kneading the rubber to give a new surface, such as an extruder, kneader, or creper When a kneaded machine is used and kneaded while supplying the chopped rubber and the epoxidized liquid, the interior can be epoxidized.

Furthermore, as a epoxidation step, after the solid rubber is treated with an epoxidation liquid, the obtained epoxidized solid rubber is kneaded with an epoxidation liquid such as a peracetic acid-containing liquid or a formic acid-containing liquid added separately as necessary. However, it is also suitable to epoxidize the epoxidized solid rubber. Also in this case, the inside can be sufficiently epoxidized by using a chopped solid rubber.
In addition, the level of epoxidation can be adjusted according to the desired physical properties as described above.

(Neutralization / washing)
The epoxidized rubber thus produced may be neutralized and washed by the same method as described above.

In addition, when the solid rubber and the epoxidized liquid are kneaded using an extruder or a kneader, the rubber size may be large. In such a state, it is difficult to clean and dry the rubber. Therefore, before the neutralization / cleaning step, it is desirable to pass the shredder again to chop the rubber.

Further, when the solid rubber and the epoxidized liquid are kneaded using an extruder or a kneader, the immersion time is secured for at least 1 hour, preferably 2 to 4 hours, in order to completely neutralize the internal acid. Is preferred. Further, when neutralized with an alkaline aqueous solution, it is desirable to wash away the liquid by showering with tap water or the like thereafter.

(Dry)
The rubber obtained above is appropriately subjected to a drying step as necessary, whereby the epoxidized natural rubber according to the present invention is obtained. This drying process can be implemented using the method similar to the above.

According to the other production method, since the solid rubber coagulated with natural rubber latex is treated with an epoxidation liquid and the solid rubber is epoxidized, the production method of epoxidized natural rubber includes the conventional production method. In comparison, epoxidized natural rubber can be produced easily and inexpensively.

Specifically, by epoxidizing a solid rubber of natural rubber, expensive chemicals used for epoxidation can be reused without waste, and loss of reagents necessary for epoxidation can be eliminated. In addition, since the conventional process of coagulating and neutralizing latex can be omitted, the manufacturing time can be greatly shortened. Furthermore, a normal epoxidized natural rubber factory requires a tank for storing latex, a reaction tank, a coagulator (for example, using water vapor), a long water tank, a dryer, etc. Since it is only necessary to add an epoxidation process to the process, it is possible to make a part of epoxidized natural rubber while making TSR, which can greatly reduce the cost. In addition, the ratio of waste liquid to the amount of rubber production is very small compared to the case of epoxidizing from latex, and it is not necessary to use various chemicals, so it is possible to reduce the environmental burden.

Further, in the method of treating the solid rubber by the other production method with an epoxidizing liquid and epoxidizing only the rubber surface, it is difficult to uniformly epoxidize the entire rubber like latex. However, when this rubber is blended alone or with another rubber, such as natural rubber or SBR, the affinity between epoxidized natural rubber and silica is improved, especially in the case of silica compounding, and the dispersibility of silica is also improved. , Tan δ is reduced and rubber strength is improved. The effect is comparable to expensive epoxidized natural rubber made from latex, but can be greatly reduced in cost.

[Epoxidized natural rubber]
The epoxidized natural rubber obtained by the production method of the present invention or the other production methods is particularly useful as a tire material.
Due to the epoxidation of natural rubber, the glass transition point of natural rubber increases. Specifically, when the degree of epoxidation increases by 1%, the glass transition point also increases by about 1 degree. When the degree of epoxidation is high, the glass transition point is greatly increased, so that the coefficient of friction when wet is increased and the braking distance when raining is shortened. On the other hand, the rolling resistance tends to be high, the fuel consumption tends to be poor, and it becomes hard at low temperatures and tends not to be suitable for, for example, winter tires. On the other hand, when the degree of epoxidation is low, the elastic modulus at a low temperature is small and can be suitably used for winter tires and the like. Moreover, the polarity of rubber | gum raises by epoxidizing, affinity with the silica used as a filler becomes high, and a fuel consumption improves. In the present invention, even when the degree of epoxidation is small as described above, the affinity with silica is sufficient and the glass transition point can be lowered, so that it can be suitably used for winter tires and the like.

[Rubber composition for tire]
Examples of the rubber composition for tires containing the epoxidized natural rubber of the present invention include a rubber component containing the epoxidized natural rubber and carbon black and / or a white filler.

In the rubber composition, the content of the epoxidized natural rubber in 100% by mass of the rubber component is preferably 5% by mass or more, more preferably 50% by mass or more, and further preferably 80% by mass or more. It may be mass%. If it is less than 5% by mass, sufficient silica dispersibility may not be obtained in silica blending.

The rubber composition may contain a rubber component other than the epoxidized natural rubber. For example, natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), styrene butadiene rubber (SBR), styrene isoprene butadiene. Examples thereof include rubber (SIBR), ethylene propylene diene rubber (EPDM), chloroprene rubber (CR), acrylonitrile butadiene rubber (NBR), and the like.

The rubber composition preferably contains silica as a white filler.
The nitrogen adsorption specific surface area (N ₂ SA) of silica is 80 m ² / g or more, preferably 100 m ² / g or more, more preferably 120 m ² / g or more. Further, N ₂ SA of silica is preferably 250 m ² / g or less, more preferably 200 m ² / g or less. By using silica in the above range, physical properties such as low fuel consumption and rubber strength can be secured.
Note that N ₂ SA of silica is a value measured by the BET method according to ASTM D3037-93.

The content of silica is preferably 10 parts by mass or more, more preferably 30 parts by mass or more with respect to 100 parts by mass of the rubber component. The content is preferably 150 parts by mass or less, more preferably 100 parts by mass or less. Within the above range, physical properties such as low fuel consumption and rubber strength can be secured.

In addition to the above materials, the rubber composition of the present invention is appropriately blended with various materials generally used in the tire industry such as zinc oxide, stearic acid, various anti-aging agents, sulfur, and vulcanization accelerators. May be.

As a method for producing the rubber composition of the present invention, known methods can be used. For example, the above components are kneaded using a rubber kneader such as an open roll or a Banbury mixer, and then vulcanized. Can be manufactured. The rubber composition can be used for each member of a tire, and in particular, can be suitably used for a tread or the like.

[Pneumatic tire]
The pneumatic tire of the present invention is produced by a usual method using the rubber composition. That is, if necessary, a rubber composition containing various materials is extruded into a shape such as a tread at an unvulcanized stage and molded by a normal method on a tire molding machine. After forming a vulcanized tire, it can be manufactured by heating and pressing in a vulcanizer.

The present invention will be specifically described based on examples, but the present invention is not limited to these examples.

[Evaluation]
In the examples, the physical properties of the prepared raw rubber and vulcanized rubber sheets were evaluated by the following methods, and the results are shown in Tables 1 to 3. The vulcanized rubber sheet was produced by the following method.
(Production of vulcanized rubber sheet)
In accordance with the formulation shown in Tables 1 to 3, a chemical other than sulfur and a vulcanization accelerator was kneaded using 1.7 L Banbury. Next, using a roll, sulfur and a vulcanization accelerator were added to the obtained kneaded product and kneaded to obtain an unvulcanized rubber composition. The obtained unvulcanized rubber composition was press vulcanized at 170 ° C. for 6 minutes to obtain a vulcanized rubber sheet.

(Measurement of degree of epoxidation)
The obtained epoxidized natural rubber was kneaded with a roll for 1 minute, sampled at several places, dissolved in toluene, reprecipitated in methanol, and dried (refined product) was used as a sample. The measurement was performed using a JNM-ECA series ¹ H-NMR apparatus manufactured by JEOL Ltd.
The degree of epoxidation (%) was calculated by the following formula.
Epoxidation degree (%) = B / (A + B) × 100
(In the formula, A is the integrated value of the peak derived from the cis proton (5.0-5.2 ppm), and B in the formula is the integrated value of the peak derived from the proton of the epoxy group (2.6-2.8 ppm)). Represents the value.)
Moreover, simply, the glass transition point of the polymer was obtained using a differential scanning calorimeter Pyris Jade DSC manufactured by PerkinElmer, and the degree of epoxidation was estimated from a calibration curve. A calibration curve was prepared from the degree of epoxidation measured by commercially available epoxidized natural rubber NMR and the glass transition point.

(Rubber strength)
Using the resulting vulcanized rubber sheet, a No. 3 dumbbell-type rubber test piece was prepared and subjected to a tensile test according to JIS K 6251 “Vulcanized rubber and thermoplastic rubber-Determination of tensile properties” to determine the breaking strength. (TB) and elongation at break (EB) were measured, and the product (TB × EB) was calculated. Comparative Example 1 by the following formula
The rubber strength (TB.times.EB) of 100 was taken as 100, and indexed by the following formula. In addition, it shows that it is excellent in rubber | gum strength, so that an index | exponent is large.
(Rubber strength index) = (TB × EB of each compound) / (Comparative Example 1)
TB x EB) x 100

(Silica dispersion)
Using the obtained vulcanized rubber sheet, the degree of dispersion of silica was measured according to the method of measuring the degree of dispersion of carbon black, ASTM D2663-B. The larger the value, the better the dispersion, with 100% being the highest. The results are represented by symbols according to the following.
A: Dispersity ≧ 97.5%
○: 97.5%> dispersion degree ≧ 95%
Δ: 95%> dispersity ≧ 92%
×: 92%> dispersion degree

Hereinafter, various chemicals used in Examples 1-1 to 1-5 and Comparative Examples 1-1 to 1-4 will be described.
Field latex (FL): Field latex collected in southern Thailand within 3 days after collection (ammonia water is added to prevent spoilage and coagulation, and the amount of ammonia is adjusted to 0.2% by mass. Drying) The rubber content is adjusted to 30%.)
Natural rubber latex: Raw ammonia latex added with anti-corrosion and stability by adding ammonia, trace amount of zinc oxide and tetrathiuram disulfide (60% dry rubber content, 0.2% ammonia content)
Surfactant A-1: Polyoxyethylene fatty acid alcohol (alcohol carbon number C ₁₂ to C ₁₈ , cloud point 70 to 80 ° C.)
Surfactant B-1: Polyoxyethylene lauryl ether sodium sulfate acetic acid: active ingredient 98%, 94% reagent primary formic acid: active ingredient 88% reagent primary hydrogen peroxide solution: 50% active ingredient, diluted appropriately Used.
Sulfuric acid: 98% active ingredient
Sodium carbonate: anhydrous sodium carbonate (purity 99% or more)
Sodium hydroxide: 98% purity
Flocculant: Cationic polymer flocculant (100% purity, strong aquatic polymer flocculant “Aron Flock C312” (polymethacrylate ester type) manufactured by MT Aqua Polymer Co., Ltd.)

Silica: Degussa Ultrasil VN3
Silane coupling agent: Si266 (bis (3-triethoxysilylpropyl) disulfide)
Zinc oxide: Type 2 zinc oxide stearate of Mitsui Mining & Smelting Co., Ltd .: Beads stearic acid manufactured by NOF Corporation Tsubaki Calcium stearate: Calcium stearate GF-200 manufactured by NOF Corporation
Oil: Palm oil Olein sulfur: Sulfur vulcanization accelerator containing 5% oil TBBS: Noxeller NS manufactured by Ouchi Shinsei Chemical Co., Ltd.
Vulcanization accelerator DPG: NOCELLER D manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.

[Production Example 1-1 Preparation of peracetic acid]
(Preparation of peracetic acid-containing liquid a-1)
A peracetic acid-containing liquid a-1 was prepared by mixing 612 g of 98% acetic acid, 850 g of 20% aqueous hydrogen peroxide, and 5 g of 98% sulfuric acid and allowing to stand at 40 ° C. for 2 days. When the peracetic acid concentration was measured, it was found that 8.3% by mass was produced. The peracetic acid concentration was measured using a peracetic acid counter PA-300 manufactured by Hiranuma Sangyo Co., Ltd.

(Preparation of peracetic acid-containing liquid b-1)
The peracetic acid-containing liquid b-1 was added to the residual liquid of the peracetic acid-containing liquid a-1 used in Example 1-1 to be described later by adding 155 g of 20% hydrogen peroxide water and leaving it at 40 ° C. for 2 days. Prepared. When the peracetic acid concentration was measured, it was found that 7.8% by mass was produced.

[Production Example 1-2 Preparation of Aqueous Surfactant A-1]
150 g of polyoxyethylene fatty acid alcohol (carbon number C ₁₂ to C _{18 of} alcohol, cloud point 75 ° C.) 150 g was dissolved in 850 g of ion-exchanged water to prepare a 15% by mass aqueous surfactant solution A-1.

[Production Example 1-3 Preparation of Surfactant Aqueous Solution B-1]
100 g of polyoxyethylene lauryl ether sodium sulfate (active ingredient 70%) was dissolved in 600 g of ion-exchanged water to prepare a 10% by mass surfactant aqueous solution B-1.

Example 1-1
60 g of aqueous surfactant solution B-1 was added to 3 kg of FL (dry rubber content 30% by mass), and then 2% by mass sulfuric acid was added to adjust the pH to 4.0. To this, 3 kg of 0.1% by mass flocculant was added to solidify the rubber in granular form. The particle size (particle diameter) was 1 mm or less for fine particles and about 5 mm for coarse particles, and was almost in the range of 1 to 3 mm. Stirring was stopped, the lower aqueous phase was almost removed, water was then added and stirred, the floated rubber was scooped and washed with water three times for washing. The size of the rubber was almost the same after washing and was almost 1 to 3 mm.
Drain the rubber containing the above water, drain the water, and immerse about 1 kg in the peracetic acid-containing liquid a-1 at an initial temperature of 30 ° C. for 10 minutes (so that the rubber is evenly immersed when immersed). Rotate the rubber and dip it while holding it down.) After pulling this up, a tap water shower was applied for 20 seconds, followed by immersion in a 2% by weight aqueous sodium carbonate solution for 10 minutes, and a tap water shower was again applied for 20 seconds. Then, it dried in 90 degreeC oven for 4 hours, and obtained the epoxidized natural rubber.

Example 1-2
To 3 kg of FL, 60 g of surfactant aqueous solution B-1 was added at room temperature, and then 360 g of sodium hydroxide aqueous solution in which 90 g of sodium hydroxide was dissolved was added and left for 24 hours with stirring. To this was added a dispersion containing 9 g of a phenolic anti-aging agent (Nocrack NS-6 manufactured by Ouchi Shinsei Chemical Co., Ltd.), and the mixture was further stirred for 2 hours. To this FL, 2% by mass formic acid was slowly added to adjust the pH to 4, and 3 kg of 0.1% by mass flocculant was added to aggregate the rubber into particles. Most of the particle diameters were about 1 to 3 mm. The operation of scooping up the agglomerates and washing with water was repeated a total of 4 times. This rubber containing water is drained, water is drained, and about 1 kg of the rubber is immersed in a peracetic acid-containing liquid a-1 prepared separately from Example 1-1 at an initial temperature of 30 ° C. for 10 minutes (during immersion). In order to soak the rubber evenly, the rubber was rotated and soaked while pressing down). After pulling this up, a tap water shower was applied for 20 seconds, followed by immersion in a 2% by weight aqueous sodium carbonate solution for 10 minutes, and a tap water shower was again applied for 20 seconds. Then, it dried in 90 degreeC oven for 4 hours, and obtained the epoxidized natural rubber.

(Example 1-3)
To 3 kg of FL, 60 g of surfactant aqueous solution B-1 was added at room temperature, and then 360 g of sodium hydroxide aqueous solution in which 90 g of sodium hydroxide was dissolved was added and left for 24 hours with stirring. To this was added a dispersion containing 9 g of a phenolic anti-aging agent (Nocrack NS-6 manufactured by Ouchi Shinsei Chemical Co., Ltd.), and the mixture was further stirred for 2 hours. To this FL, 2% by mass formic acid was slowly added to adjust the pH to 4, and 3 kg of 0.1% by mass flocculant was added to aggregate the rubber into particles. Most of the particle diameters were about 1 to 3 mm. The operation of scooping up the agglomerates and washing with water was repeated a total of 4 times. The rubber containing water was soaked in a 2% by weight aqueous sodium carbonate solution for 1 hour, and then washed with tap water for 20 seconds. The rubber was drained, water was drained, and about 1 kg of the rubber was immersed in a peracetic acid-containing liquid a-1 prepared separately from Examples 1-1 and 1-2 at an initial temperature of 30 ° C. for 10 minutes (during immersion). In order to soak the rubber evenly, the rubber was rotated and soaked while pressing down). After pulling this up, a tap water shower was applied for 20 seconds, followed by immersion in a 2% by weight aqueous sodium carbonate solution for 10 minutes, and a tap water shower was again applied for 20 seconds. Then, it dried in 90 degreeC oven for 4 hours, and obtained the epoxidized natural rubber.

(Example 1-4)
60 g of surfactant aqueous solution B-1 was added to 3 kg of FL, and then 2 mass% sulfuric acid was added to adjust the pH to 4.0. To this, 3 kg of 0.1% by mass flocculant was added to solidify the rubber in granular form. The particle size was 1 mm or less for fine particles and about 5 mm for coarse particles, and was almost in the range of 1 to 3 mm. Stirring was stopped, the lower aqueous phase was almost removed, water was then added and stirred, the floated rubber was scooped and washed with water three times for washing. The size of the rubber was almost the same after washing and was almost 1 to 3 mm.
Drain the rubber containing the above water, drain the water, and immerse about 1 kg in peracetic acid-containing liquid b-1 at an initial temperature of 30 ° C. for 10 minutes (so that the rubber is immersed evenly when immersed). Rotate the rubber and dip it while holding it down.) After pulling this up, a tap water shower was applied for 20 seconds, followed by immersion in a 2% by weight aqueous sodium carbonate solution for 10 minutes, and a tap water shower was again applied for 20 seconds. Then, it dried in 90 degreeC oven for 4 hours, and obtained the epoxidized natural rubber.

(Example 1-5)
60 g of surfactant aqueous solution B-1 was added to 3 kg of FL, and then 2 mass% sulfuric acid was added to adjust the pH to 4.0. To this, 3 kg of 0.1% by mass flocculant was added to solidify the rubber in granular form. The particle size was 1 mm or less for fine particles and about 5 mm for coarse particles, and was almost in the range of 1 to 3 mm. Stirring was stopped, the lower aqueous phase was almost removed, water was then added and stirred, the floated rubber was scooped and washed with water three times for washing. The size of the rubber was almost the same after washing and was almost 1 to 3 mm.
The above-mentioned rubber containing water was transferred to a formic acid aqueous solution in which 2 kg of scooping ion exchange water and 920 g of formic acid were mixed. To this, 500 g of 50 mass% hydrogen peroxide was slowly added. After 5 hours, the rubber was taken out and subjected to a tap water shower for 20 seconds, then immersed in a 2% by weight aqueous sodium carbonate solution for 10 minutes, and then a tap water shower was again applied for 20 seconds. Then, it dried in 90 degreeC oven for 4 hours, and obtained the epoxidized natural rubber.

(Comparative Example 1-1)
Add 440 g of distilled water to 500 g of low ammonia natural rubber latex with a dry rubber content of 60% by mass (of which 300 g of dry rubber), add 60 g of surfactant aqueous solution A-1 (9 g of active ingredient), and slowly add 2 Stir for minutes. While stirring this with a stirrer, 52.3 g of formic acid (88% by mass) was slowly added, and further 93.5 g of hydrogen peroxide was added over 3 hours using a tube pump. The temperature of the latex started from 40 ° C., and exceeded 60 ° C. when the reaction progressed. Therefore, the reaction was carried out while cooling the surroundings so as to be 60 to 65 ° C. Sampling 4 hours, 8 hours, and 24 hours from the start of hydrogen peroxide water addition, the rubber is coagulated with water vapor, neutralized with a 2% by weight aqueous sodium carbonate solution for 16 hours, and then dried and epoxidized. The degree of epoxidation was examined by NMR. As a result, the degree of epoxidation was 12.5% in 4 hours, 18.5% in 8 hours, and 25.4% in 24 hours. Although epoxidized, it took a very long time. Further, since formic acid is contained in rubber at the time of coagulation, it cannot be reused, and a surfactant is used, so that its cost also increases. Furthermore, if the surfactant remains, it absorbs water and deteriorates the physical properties of the rubber, so it has been necessary to wash it very carefully.

(Comparative Example 1-2)
460 g of distilled water was added to 500 g of low ammonia natural rubber latex having a dry rubber content of 60% by mass (of which 300 g of dry rubber was added), and 40 g of surfactant aqueous solution A-1 (6 g of active ingredient) was added slowly with a spatula. Stir for minutes. This latex was fed into the mixing device (size: 25 cc) at a rate of 10.0 g / min using a tube pump (tube inner diameter: 4 mm) with adjusted liquid feeding amount. It was fed into the mixing apparatus so as to be 6 g / min. After sufficiently mixing them using a stirring blade in the mixing apparatus, the liquid is fed to the coagulation apparatus by a tube pump (inner diameter of the tube 5 mm) adjusted so that the liquid feeding amount is 17.6 g / min (850 mm / min). did. The temperature of the mixed solution at the time of mixing was 25 ° C., and the temperature of the mixed solution at the time of feeding was 55 ° C. Since the liquid was hardly stored in the mixing apparatus, there was almost no time for the liquid to stay in the mixing apparatus. On the other hand, the residence time in the tube was 15 minutes. In the coagulation apparatus, a certain amount of water vapor is blown from the bottom, and from the top, the mixed liquid descends along the wall. The latex coagulated with water vapor while falling down and partially separated into rubber and serum. The rubber coming out of the coagulator is sampled every 10 minutes, cooled with water, immersed in an aqueous solution of 1 to 3% by weight of sodium bicarbonate for a whole day and then washed again with water, dried to a constant weight, The degree of epoxidation of the produced rubber was examined by NMR.
As a result, the degree of epoxidation was 25.1%, 25.3%, 25.1%, 25.4%, 25.4%, 25.7%, 25.3%, 25.5%, It was confirmed to be stable. Although the reaction is proceeding very quickly, the overall cost is very high because the loss of material is very large, water vapor that consumes a lot of energy is used, and it takes a lot of time for neutralization and washing. .

(Comparative Example 1-3)
A vulcanized rubber sheet was prepared in the same manner as in Example 1-1 except that TSR20 was used, and the physical properties were examined.

(Comparative Example 1-4)
To 3 kg of FL, 2% by mass sulfuric acid was added to coagulate the rubber. The rubber became a large lump with a diameter of about 20 cm. Therefore, epoxidation of the whole was impossible, and the subsequent epoxidation process was abandoned.

As is apparent from Table 1, in the production methods of the examples, the reaction was much faster than that of Comparative Example 1-1, and the cost required for epoxidation was low. In addition, even when the amount of epoxidation is relatively small, the dispersibility of silica has reached the same level as the manufacturing method of the comparative example with a long reaction time and high cost, and has the characteristics that the rubber strength is also high. . Further, in the examples, a uniform epoxidized natural rubber was obtained in the same manner as in the method of epoxidation in the latex state.

Hereinafter, various chemicals used in Examples 2-1 to 2-11 and Comparative Examples 2-1 to 2-4 will be described.
Natural rubber latex: Raw ammonia latex added with anti-corrosion and stability by adding ammonia, trace amount of zinc oxide and tetrathiuram disulfide (60% dry rubber content, 0.2% ammonia content)
Cup lamps: Common ones collected in the Tohoku region of Thailand and sold to TSR processing plants that have been processed in the normal TSR manufacturing process (slab cutters, prebreakers, rotary cutters, etc.) Afterwards, solid rubber shredded to about 1 to 3 mm with a creper and a shredder)
Surfactant: Polyoxyethylene fatty acid alcohol (alcohol carbon number C ₁₂ to C ₁₈ , cloud point 70 to 80 ° C.)
Acetic acid: active ingredient 98%, 94% reagent primary formic acid: active ingredient 88% reagent primary hydrogen peroxide solution: active ingredient 50% and 30% (50% when no concentration is indicated)
Sulfuric acid: 98% active ingredient
Sodium carbonate: anhydrous sodium carbonate (purity 99% or more)

[Production Example 2-1 Preparation of Peracetic Acid]
(Preparation of peracetic acid-containing liquid a-2)
A peracetic acid-containing liquid a-2 was prepared by mixing 243 g of 98% acetic acid, 270 g of hydrogen peroxide solution, and 4 g of sulfuric acid and allowing to stand at 40 ° C. for 1 day. When peracetic acid was quantified by titration, it was found that 60.4 g was produced.

(Preparation of peracetic acid-containing liquid b-2)
A peracetic acid-containing liquid b-2 was prepared by adding 54 g of hydrogen peroxide water to the residual liquid of the peracetic acid-containing liquid a-2 used in Example 2-1 to be described later and allowing to stand at 40 ° C. for 1 day. . When peracetic acid was quantified by titration, it was calculated that 59 g of peracetic acid was generated in the whole liquid.

(Preparation of peracetic acid-containing liquid c-2)
A peracetic acid-containing liquid c-2 was prepared by adding 61 g of hydrogen peroxide water to the residual liquid of the peracetic acid-containing liquid b-2 used in Example 2-4, which will be described later, and allowing it to stand at 40 ° C. for 1 day. . When peracetic acid was quantified by titration, it was calculated that 58 g of peracetic acid was generated in the whole liquid.

(Preparation of peracetic acid solution d-2)
A peracetic acid-containing liquid d-2 was prepared by mixing 500 g of 94% acetic acid, 887 g of 30% aqueous hydrogen peroxide, and 4 g of sulfuric acid and allowing to stand at 40 ° C. for 1 day. When peracetic acid was quantified by titration, it was found that 95.2 g of peracetic acid was produced as a whole. In Example 2-11, all of the reagent amounts were prepared 10 times and used.

[Production Example 2-2 Preparation of aqueous surfactant solution]
150 g of polyoxyethylene fatty acid alcohol (carbon number C ₁₂ to C _{18 of} alcohol, cloud point 75 ° C.) 150 g was dissolved in 850 g of ion-exchanged water to prepare a 15% by mass aqueous surfactant solution.

Example 2-1
3 kg of a cup lamp (water content 29%) was immersed in 517 g of peracetic acid-containing liquid a-2 for 5 minutes at a temperature of 30 ° C. (When soaking, rotate the rubber so that the rubber is immersed evenly, soak it while pressing it down) ) After pulling this up, a tap water shower was applied for 20 seconds, then immersed in a 2% aqueous sodium carbonate solution for 5 minutes, and a tap water shower was again applied for 20 seconds. Then, it dried in 90 degreeC oven for 4 hours, and obtained the epoxidized natural rubber.

(Example 2-2)
Epoxidized natural rubber was obtained in the same manner as in Example 2-1, except that the amount of peracetic acid-containing liquid a-2 was changed to 1034 g.

(Example 2-3)
An epoxidized natural rubber was obtained in the same manner as in Example 2-1, except that the amount of the peracetic acid-containing liquid a-2 was changed to 2067 g.

(Example 2-4)
An epoxidized natural rubber was obtained in the same manner as in Example 2-1, except that the peracetic acid-containing liquid a-2 was changed to the peracetic acid-containing liquid b-2.

(Example 2-5)
An epoxidized natural rubber was obtained in the same manner as in Example 2-1, except that the peracetic acid-containing liquid a-2 was changed to a peracetic acid-containing liquid c-2.

(Example 2-6)
30 kg of a cup lamp (water content 29%) was immersed in 5.17 kg of peracetic acid-containing liquid a-2 for 5 minutes at a temperature of 30 ° C. (Rotating and pressing the rubber so that the rubber was evenly immersed when immersed) I was immersed in it). After pulling this up, the rubber pulled into the extruder and 10.34 kg of peracetic acid-containing liquid a-2 (peracetic acid concentration prepared separately from the above-mentioned soaked one is 10% by mass or more) are added in small amounts. Then, udon-like rubber was obtained from the extruded plate having holes. This was subjected to a tap water shower for 20 seconds, then immersed in a 2% aqueous sodium carbonate solution for 5 minutes, and then again a tap water shower for 20 seconds. Then, it dried in 90 degreeC oven for 4 hours, and obtained the epoxidized natural rubber.

(Comparative Example 2-1)
A rubber was produced in the same manner as in Comparative Example 1-1.

(Comparative Example 2-2)
460 g of distilled water is added to 500 g of low ammonia natural rubber latex having a dry rubber content of 60% by mass (of which 300 g of dry rubber is added), and 40 g of a 15% by mass aqueous surfactant solution (6 g of active ingredient) is further added with a spatula. And stirred for 2 minutes. This latex was fed into the mixing device (size: 25 cc) at a rate of 10.0 g / min using a tube pump (tube inner diameter: 4 mm) with an adjusted feed rate, and 7 peracetic acid-containing solution a-2 was simultaneously introduced. It was fed into the mixing apparatus so as to be 6 g / min. After sufficiently mixing them using a stirring blade in the mixing apparatus, the liquid is fed to the coagulation apparatus by a tube pump (inner diameter of the tube 5 mm) adjusted so that the liquid feeding amount is 17.6 g / min (850 mm / min). did. The temperature of the mixed solution at the time of mixing was 25 ° C., and the temperature of the mixed solution at the time of feeding was 55 ° C. Since the liquid was hardly stored in the mixing apparatus, there was almost no time for the liquid to stay in the mixing apparatus. On the other hand, the residence time in the tube was 15 minutes. In the coagulation apparatus, a certain amount of water vapor is blown from the bottom, and from the top, the mixed liquid descends along the wall. The latex coagulated with water vapor while falling down and partially separated into rubber and serum. Sample the rubber coming out of the coagulator every 10 minutes, cool it with water, immerse it in a 1 to 3% aqueous solution of sodium bicarbonate for a whole day and then wash it again and dry it to a constant weight. The degree of epoxidation of the resulting rubber was examined by NMR. As a result, the degree of epoxidation was 25.1%, 25.3%, 25.1%, 25.4%, 25.4%, 25.7%, 25.3%, 25.5%, It was confirmed to be stable. Although the reaction is proceeding very quickly, the overall cost is very high because the loss of material is very large, water vapor that consumes a lot of energy is used, and it takes a lot of time for neutralization and washing. .

(Comparative Example 2-3)
440 g of distilled water is added to 500 g of low ammonia natural rubber latex having a dry rubber content of 60% by weight (of which 300 g of dry rubber is added), and 60 g of a 15% by weight aqueous surfactant solution (9 g of active ingredient) is added slowly with a spatula. And stirred for 2 minutes. While stirring with a stirrer, 9.18 g of acetic acid (98%) was slowly added, and 34 g of hydrogen peroxide (30%) was further added using a tube pump over 3 hours. The temperature of the latex started from 40 ° C., and when the reaction progressed, it might exceed 60 ° C. Therefore, the reaction was carried out while adjusting the ambient temperature to be 60 to 65 ° C. Sampling 4 hours, 8 hours, 20 hours, 24 hours, and 27 hours from the start of hydrogen peroxide water addition, the rubber was coagulated with water vapor, neutralized and dried, and the epoxidation degree of the produced rubber was measured by NMR. The degree of epoxidation was examined. As a result, the degree of epoxidation was 1.5% at 4 hours, 3.2% at 8 hours, 4.6% at 20 hours, 4.9% at 24 hours, and 5.1% at 27 hours. Although the process gradually progressed gradually, it took a very long time. Moreover, all the used reagents were uncollectable, and the process was very long and costly as in Comparative Example 2.

(Comparative Example 2-4)
A vulcanized rubber sheet was prepared in the same manner as in Example 2-1, except that TSR20 was used, and the physical properties were examined.

As is clear from Table 2, in the production methods of the examples, the reaction was very fast and the cost required for epoxidation was low. In addition, even when the amount of epoxidation is relatively small, the dispersibility of silica has reached the same level as the production method of the comparative example with a long reaction time and high cost, and has the characteristics of high rubber strength. .

(Example 2-7)
Add 3 kg of ion-exchanged water and 5 g of sulfuric acid to 3 kg of 88% formic acid aqueous solution in a jacketed container, stir it, soak 3 kg of cup lamp (moisture content 29%), and heat it so that the total temperature is 50 ° C. did. The 30% hydrogen peroxide solution 118g was dripped here in 3 hours, and it was made to react for 5 hours. After pulling it up, it was subjected to a tap water shower for 20 seconds, then dipped in a 2% aqueous sodium carbonate solution for 10 minutes, again showered with tap water for 20 seconds, and then dried. Drying was carried out in an oven at 90 ° C. for 4 hours to obtain an epoxidized natural rubber.

(Example 2-8)
Epoxidized natural rubber was obtained in the same manner as in Example 2-7, except that 197 g of 30% hydrogen peroxide was used.

(Example 2-9)
Epoxidized natural rubber was obtained in the same manner as in Example 2-7 except that 394 g of 30% hydrogen peroxide was used.

(Example 2-10)
An epoxidized natural rubber was obtained in the same manner as in Example 2-7, except that 789 g of 30% hydrogen peroxide was used.

(Example 2-11)
Add 3 kg of ion-exchanged water and 5 g of sulfuric acid to 3 kg of 88% formic acid aqueous solution in a jacketed container, stir it, soak 3 kg of cup lamp (moisture content 29%), and heat it so that the total temperature is 50 ° C. did. To this, 394 g of 30% hydrogen peroxide solution was dropped over 3 hours and reacted for 5 hours. After pulling this up, the epoxidation was carried out while gradually introducing into the extruder together with the peracetic acid-containing liquid d-2 and kneading. A plate with a hole is attached to the exit of the extruder, the udon-like rubber that has come out is washed with water, immersed in a 2% aqueous sodium carbonate solution for 2 hours, and then sprayed with water again to wash away the alkali, and then shredder And then dried at 90 ° C. for 4 hours to obtain an epoxidized natural rubber.

As is apparent from Table 3, also in Examples 2-7 to 2-11, epoxidation was possible very easily, and the cost required for epoxidation could be reduced. Further, as described above, even those having a relatively small amount of epoxidation exhibited high silica dispersibility and excellent rubber strength.

Claims

An epoxidized natural rubber comprising a step 1 for coagulating natural rubber latex into a granular form to prepare a granular solid rubber, and a step 2 for treating the obtained granular solid rubber with an epoxidizing liquid and epoxidizing the granular solid rubber Manufacturing method.
The method for producing an epoxidized natural rubber according to claim 1, wherein the epoxidized liquid is a peracetic acid-containing liquid and / or a formic acid-containing liquid.
The method for producing an epoxidized natural rubber according to claim 2, wherein the peracetic acid-containing liquid is obtained by mixing and reacting acetic acid and / or acetic anhydride and hydrogen peroxide.
The method for producing an epoxidized natural rubber according to claim 2, wherein the liquid formic acid-containing liquid is obtained by mixing and reacting formic acid and hydrogen peroxide.
The natural rubber latex is at least one selected from the group consisting of field latex, concentrated latex obtained by concentrating field latex, and modified natural rubber latex obtained by removing non-rubber components therefrom. A process for producing an epoxidized natural rubber according to claim 1.
The method for producing an epoxidized natural rubber according to any one of claims 1 to 5, wherein the step 1 comprises solidifying the natural rubber latex into a granular form using an acid to prepare a granular solid rubber.
The method for producing an epoxidized natural rubber according to any one of claims 1 to 5, wherein in the step 1, the natural rubber latex is coagulated into particles using an acid and a flocculant to prepare a granular solid rubber.
The method for producing an epoxidized natural rubber according to any one of claims 1 to 7, wherein the particle size of the granular solid rubber is 20 mm or less.
The method for producing an epoxidized natural rubber according to any one of claims 1 to 7, wherein a particle diameter of the granular solid rubber is 12 mm or less.
An epoxidized natural rubber obtained by the production method according to any one of claims 1 to 9.
The epoxidized natural rubber according to claim 10, which has an epoxidation degree of 0.1 to 50%.
A rubber composition for tires comprising the epoxidized natural rubber according to claim 10 or 11.
A pneumatic tire produced using the tire rubber composition according to claim 12.